Biological cells, the basic building blocks of all life forms, are surrounded by a lipid membrane. More than half of the membrane is occupied by membrane proteins, which can regulate the cell... Show moreBiological cells, the basic building blocks of all life forms, are surrounded by a lipid membrane. More than half of the membrane is occupied by membrane proteins, which can regulate the cell functionality through specific arrangements. To regulate the arrangements several proteins have to work together. In addition to direct forces, there exists an indirect force between the proteins, which stems from their deformation of the membrane and contributes to their self-organization. Since the actual membrane is very crowded and proteins are too tiny and complex to measure this interaction, in this thesis we used a model system consisting of lipid membranes and solid particles to study the deformation-mediated interaction. We experimentally confirmed for the first time that, unlike many known forces, this deformation-mediated interaction is not additive, i.e. the strength and range of three (or more) deformations cannot be obtained by simple addition of the interactions between pairs of deformations. We found that the interaction weakens with increasing number of membrane-deforming particles and that the particle become less ordered. We investigated deformations in both directions of the membrane and found that the interaction can be both repulsive and attractive, and furthermore depends on the shape of the deformation. This thesis helps to better understand the organization of proteins that deform cellular membranes. Show less
Supramolecular polymers are class of materials that are formed by non-covalent interactions such as hydrogen bonding, π-π interactions, electrostatic interactions and the hydrophobic effect. The... Show moreSupramolecular polymers are class of materials that are formed by non-covalent interactions such as hydrogen bonding, π-π interactions, electrostatic interactions and the hydrophobic effect. The design and development of supramolecular polymers in aqueous solution gained a particular attention for the wide variety of applications in the biomedical field. In water, the self-assembly of well-defined nanostructures is mainly determined by the combination of hydrophobic effect with hydrogen bonding interactions in the monomer design. When squaramide-based monomer self-assemble, the formation of stable nanostructures in water is determined by the formation of directional hydrogen bonds which are strengthened by the partial aromatic character of the squaramide. In this thesis, the self-assembly properties of a panel of squaramide-based monomers is examined in aqueous solution through modulating the monomer chemical structure, co-assembly and introduction of light responsive chemistries. Show less
This thesis aims to improve the detection from ultra-weak single emitter by enhancing their emission properties with plasmonic nanostructures. We exploit the wet-chemically synthesized single... Show moreThis thesis aims to improve the detection from ultra-weak single emitter by enhancing their emission properties with plasmonic nanostructures. We exploit the wet-chemically synthesized single crystalline gold nanorods (GNRs) as our basic frameworks in the whole studies, simply because of their unique optical properties, such as the intense electromagnetic fields enhancement near the tips, and the narrow, tunable resonance with light. We first explore the lower limit of fluorescence quantum yield for single-molecule detection by enhancing the fluorescence with a single gold nanorod. Later, we develop a method to synthesize end-to-end gold nanorod dimers on glass substrates with the aid of molecular linkers, and then apply these strong plasmon coupling systems to enhance the single-molecule fluorescence under two-photon excitation. Show less
In this thesis, the researcher developed a nanosystem based on the metallophilic Interaction between cyclometalated complexes. Using this strategy, the researcher achieved efficient photodynamic... Show moreIn this thesis, the researcher developed a nanosystem based on the metallophilic Interaction between cyclometalated complexes. Using this strategy, the researcher achieved efficient photodynamic therapy to several cancers, accompanied by the cell imaging property. Show less
Despite the fact that gold nanoparticles (GNPs) are one of the most studied nanoparticles, there is still a necessity for new approaches allowing for effective protective coating to enable wider... Show moreDespite the fact that gold nanoparticles (GNPs) are one of the most studied nanoparticles, there is still a necessity for new approaches allowing for effective protective coating to enable wider use of GNPs in biomedical applications. This dissertation is focusing on the use of self-assembling peptide amphiphiles as stabilizers for spherical GNPs and gold nanorods (GNRs). Peptide amphiphiles stabilize GNPs and GNRs through formation of a self-assembled monolayer on their surface. These gold-peptide amphiphile conjugates are stable under (and beyond) physiologically relevant conditions, do not induce cytotoxicity, and can be readily modified with ligands of interest. To demonstrate the potential of these conjugates, they were used to study T-cell mediated immune responses as function of GNP size and shape. It was shown that GNRs deliver more antigen to the lysosomes and induce better T-helper responses, while larger particles were more effective at mediating antigen delivery to the cytosol, thus inducing better cytotoxic responses. Show less
This thesis is concerned with the constitution of chiral responsive matrix assemblies that may undergo light-driven conformational changes and self-select vibrations to develop vibronic states for... Show moreThis thesis is concerned with the constitution of chiral responsive matrix assemblies that may undergo light-driven conformational changes and self-select vibrations to develop vibronic states for driving semi-classical coherent transfer with nearly 100% yield in a lossless NCAP process. In this work, a truncated CsmA derived from the CsmA protein from the baseplate of the Chlorobaculum tepidum has been used to engineer a chiral matrix around a zinc protoporphyrin IX (ZnPP) chromophore (Chapter 2). After the study of the specific structure of tCsmA-ZnPP complex, the mechanism of self-assembly was resolved (Chapter 3 and Chapter 4). Expression and purification of tCsmA in E.coli was explored to pave the way for other methods, such as NMR (Chapter 5). Show less
The aim of this thesis is to develop and study a robust and adaptable scaffold for supramolecular polymer self-assembly in water. For this purpose, I rely on the use of squaramides to provide... Show moreThe aim of this thesis is to develop and study a robust and adaptable scaffold for supramolecular polymer self-assembly in water. For this purpose, I rely on the use of squaramides to provide directional interactions in order to drive the formation of one-dimensional aggregates through self-assembly. The interplay of hydrogen-bonding and aromaticity in the monomer self-assembly process is explored in the squaramide unit, by examining the consequence of aromatic gain on this process. Additionally, by systematic modification of the monomer structure, a library of supramolecular structures with different morphologies is developed and their use as future drug nanovehicles is studied in an in vivo model involving zebrafish embryos. Show less
For more than 65 years, scientists have been fascinated by the idea to miniaturize electrical circuits toward the smallest length scales. One particular way is inspired by nature itself,... Show moreFor more than 65 years, scientists have been fascinated by the idea to miniaturize electrical circuits toward the smallest length scales. One particular way is inspired by nature itself, specifically to assemble electrical components and switches from atoms and molecules. The molecules typically used have dimensions of the scale of a few nanometers (1 nanometer = 0,000000001 meter). The scientific research area that represents the study of electrical currents through molecules is called "molecular charge transport" or "molecular electronics". In this thesis, I have performed fundamental research on charge transport through various molecules. Specifically, I have investigated a special type of molecule that has the ability to change its spin state. To test these functional molecules, I have used a more robust type of molecular device that enables me to bridge the size gap mentioned above. This thesis has led to two important new insights. First, the properties of a switchable molecular device can be strongly enhanced artificially by making use of a charge transport mechanism called multiple inelastic cotunneling. Second, we show that the spin transition phenomenon can take place in a molecular-nanoparticle ensemble. Show less
DNA-hosted silver clusters (Ag:DNAs) have attracted a lot of attention due to their small size (~20 atoms), wide range of applications in chemistry and biology, and sequence-dependent optical... Show moreDNA-hosted silver clusters (Ag:DNAs) have attracted a lot of attention due to their small size (~20 atoms), wide range of applications in chemistry and biology, and sequence-dependent optical tunability. Most of the previous studies are focused on the ensemble of emitters in solution. However, little is known about the optical properties of individual emitters, which is a crucial step towards understanding of their real nature, otherwise lost in ensemble averaging. We show that the excitation and emission spectra of individual emitters are broad even at 1.7 K (FWHM ~25 nm). Also, polarization measurements indicate that the excitation is not strongly dependent on the polarization of excitation light, whereas the emission is highly linearly polarized. Furthermore, from time-resolved measurements, we can conclude that the emission of single emitters can be fitted with single exponential decay curve, whereas the emitters organized with nanometer precision on the DNA scaffolds show double–exponential decay. This indicates the interaction between densely packed Ag:DNAs. Finally, we show that the DNA tubes can be used as a nano-contact glue between the colloidal particles functionalized with short DNA strands. Show less
The growing field of bio-electronics holds many promises with regard to the integration of various organic molecules onto printed circuit-boards. These include a decrease in the cost of production,... Show moreThe growing field of bio-electronics holds many promises with regard to the integration of various organic molecules onto printed circuit-boards. These include a decrease in the cost of production, an increased sensitivity and specificity to molecular detection from various solutions (i.e. blood) and ultra-miniaturization. However, numerous challenges still face such prospects, chief among which is the retention of biological activity of the adsorbed molecules. To circumvent the possible harmful effects of the bare surfaces, we have made use of self-assembled molecular films that not only shield the proteins (i.e. azurin) off surfaces, but also help establish a spatially-defined conductive path to electrodes. At the same time, the protein itself was engineered such that the active cavity is directly connected via such molecular __wires__. Our results may help in the adsorption of more complex enzymes into future molecular devices, that will retain their activity on the surfaces and are able to integrate into biosensors. Show less
Of the various biomolecular building blocks in use in nature, coiled-coil forming peptides are amongst those with the most potential as building blocks for the synthetic self-assembly of... Show moreOf the various biomolecular building blocks in use in nature, coiled-coil forming peptides are amongst those with the most potential as building blocks for the synthetic self-assembly of nanostructures. Native coiled coils have the ability to function in, and influence, complex systems composed of multiple building blocks. However, there have only been a limited number of synthetic coiled-coil assemblies that mimic native coiled coils by incorporating multiple assembling components. This thesis represents efforts at extending this aspect of coiled-coil self-assembly. In order to achieve this, a range of hybrid molecules were synthesized which combine coiled-coil peptides with a hydrophobic component. In this way the highly specific coiled-coil self-assembly is juxtaposed with the non-specific, but structure-inducing aggregation of the hydrophobic section. This thesis asked simple questions: can coiled coils function when covalently attached to large hydrophobic blocks? How large can the hydrophobic blocks be? Can coiled coils function when incorporated noncovalently with a supramolecular assembly? By answering these fundamental questions the possibilities of prescriptive self-assembly have been probed and expanded, novel preparative methods have been developed, and specific applications have arisen. Show less
